Abstract Silver nanoparticles (AgNPs) are increasingly drawing a great deal of attention because of their exclusive properties and a huge variety of applications. In recent years, using AgNPs supported on various carriers as heterogeneous catalysts has become promising for treating some toxic gases in the environment, such as HCHO. This study has successfully synthesized AgNPs onto ZSM-5 microporous zeolite and ZSM-5 mesopore-modified zeolite (Meso-ZSM-5) by ion-exchange method using sodium borohydride as a reducing agent. The resulting catalysts were then characterized by N 2 adsorption-desorption method. In order to evaluate HCHO adsorption, desorption, and the surface reaction of these catalysts, temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) were employed. The TPD and TPSR experiments were conducted with different relative humidity. The results showed that Ag/Meso-ZSM-5 exhibited higher catalyst activity in HCHO complete oxidation than Ag/ZSM-5 at high temperatures because of a new larger pore system within the zeolite. Furthermore, TPD and TPSR experiments provided an explanation for the poor performance of the catalysts at low temperatures, which was associated with the high adsorption capacity of the zeolite.